Method of producing valuable liquid fuels



May 23, 1933. MPH-:R ErAL 1,910,050

METHOD OF PRODUCING VALUABLLIQUID FUELS- Filed April 8, 19,29`

- 195 MJT ATTORNEYS mentedlmay 23, less UNITED 'STATES' PATENT OFFICE umPIER; OIHEIDELBEBG, EUGEN ANTHES, 0F EUDWIGBHAlN-ON-'IHE-m AID .LUGUHEEIBENIUT, 0l' WEBLINGEN, GERM-NY, ASSIGNOBS, BY HEBNE AS- SIGmm T0STANDARD-I. G. OOIPAN'Y, 0F lLINDEN', NEW JERSEY, CORPORA- T101' OI'DELAWARE IETHOD 0l' .PBDDUGING VALUABLE IiIQUID FUELS application neaapra s, 1929, serial ne.

terials into two portions, one of which is richer and one of which ispoorer in hydrogen, 1 by treatment with solvents in which the solubilityof the said portions is considerably diierent, the .first portion, richin hydrogen, being partially or wholly suitable for employment asilluminating oil or Diesel oil, elther 2 directly or aftertreatment withhydrogen under pressure and atan elevated temperature, and the secondfraction poorer in hydrogen beingsubjected to a destructivehydrogenation -under a pressure of at least 50'at- 25 mospheres, eitheralone or together with other carbonaceous substances, orv even with apart of the portion rich in hydrogen therebfy ob taining a non-knockingmotor fuel o low boiling point.

w It is preferable to work in such a manner that the constituents of theaturc of middle oils are-separated from the initial materials, in so faras the latter are 'not themselves middle oils, and that these are thenseparated by 85 treatment with solvents into constituents rich inhydrogen and suitable as illuminating oils and Diesel oils, and'constituents rer in hydrogemthe latter being or remaining dissolved inthe solvent, whereas the former 5 forms ,a layer thereon, which latterare then,

as .already described, converted into a. nonknocking motor fuel bytreatment withhy-l drogen, if desired together with the constitui entsremaining after the separation of the' middle oils.

anasss. anim Germany apru as, 192s.

Li uid sulphur dioxide or liquid ammonia, ifldeslred in admixture'withcyclohexane, or methanol orv both may be advantageouslyemployed as thesolvent. The process may be carried out, for example, by subjecting themiddle oils to extraction with liquid sulphur dioxide, whereby theconstituents poor in hydrogen, and in particular the aromatichydrocarbons, are dissolved. The extraction agent, after separationlfrom the extracted constituents for example by od may he employed again.A

The process in accordance with the present invention is attended byconsiderable advantages. The constituents rich in hydrogen, forexample,of the products of 'medium' boiling point obtained by thedestructive hydrogenation of various kinds of coal, tars, mineral oilsand the like, constitute excellent illuminating oils which do not giverise to the formation of carbon deposits and which comply entirely Ewith the standards for such oils. They are also' excellently suitablefor employment as Diesel oils.`

'The extracted constituents poor in hydrogen and containing inparticular aromatic compounds are subjected Yto a treatment withhydrogen either alone or together with other carhonaceous substances,for example those which remain after the separation of the middle oilsfrom mineral oils, destructive hydrogenation products Yor the like, the'treatment preferably being under pressure.

tained in which the ratio of the amounts of 'aromatic hydrocarbons tothose of the other Good benzines are also obtained by subjecting thevconconstituents is very satisfactory.

stituents poor in hydrogen to destructive hydrogenation together withother carbonaceous Y Non- Y knocking. motor fuels can then readily beoby ratedproduct;

source, for example with benzine arising from the destructivehydrogenation of brown coal rich in bitumen.

It is preferable to carry out the destructive hydrogenation-or theseparate stages thereof in the presence of catalysts, in particularthose immune to i poisoning by sulphur and in particular those from thesixth group of the periodic system. thThe products poor in hydrogenobtained by e advantage for the extraction of valuable products fromvarious kinds of coal, and the like, under pressure, or for the workingup of oleiferous residues obtained in the destructive hydrogenation ofcoa-l.`

An apparatus for carrying out the process according to the presentinvention is further illustrated in vertical cross-section by way ofexample in the accompanying drawing, though it should be understood thatthe invention is not limited to operating in the specific apparatusillustrated. In the drawingc is a mixing device; a is a pipe for theintroduction of carbonaceous material into said device; b. is a pipe forthe introduction of solvent, and s is a stirrer in said mixing device,which is set in motion by the driving wheel g and the bevel gear 1'. ois a separating vessel in which the treated materials separate into twolayers; y is a spy-glass; e is a pipe for drawing oi the upper layerfrom the said separating vessel; f is a vessel for the separation of thesolvent from the sepag is a pipe for the return of the solvent; 71. is acompressor for reliquefying the solvent; j is a compressor; k is a pipefor the introduction of hydrogen; lis a heating coil; m is ahigh-pressure reaction vessel; n is a condenser and o is a separatingvessel.

-In the operation of the process the liquid carbonaceous material to betreated is introduced into the mixing vessel o by way of the pipe aand asolvent in which the solubility of the-portion poorer in hydrogen isconsiderably different from that of the portion richer in hydrogen isintroduced into the mixing vessel by way of the pipe b, The materialsare well mixed by the stirrer c, actuated by the driving wheel g and thebevel gear 1'. The mixture is then passed into the separating vessel ofitted with the spy-glass y in which the mixture separates into twolayers, the upper layer consisting of the portion rich in hydrogen andthe lower layer of the solution 'of the portion poor in hydrogen in thesolvent-in cases where the solvent is of 'such a nature that the portionof the carbonaceous material poor in hydrogen dissolves therein and thatthe solution obtained is denser than the portion rich in hydrogen. Theformer is drawn oi by way of the pipe e. 'I 'he solution of the portionpoor in hydrogen 1s drawn oli into the vessel f in which the solvent isextraction may also be employed with' evaporated and returned for use byway of the pipe g. The solvent is reliqueed in the compressor k andreturned to the process. The portion poor in hydrogen remaining in thevessel f is passed to the compressor j, and hydrogen having the samepressure is introduced at la. The mixture'is preheated to the desiredtemperature in the coil l and is then passed into the high pressurereaction vessel n. The reaction products issu.- ing from the said vesselare cooled in the condenser n and passed into the stripping vessel o.The unused hydrogen is removed through the vessel p and may be returnedto.

the process. v

The following examples will further illustrate the nature of thisinvention, but the invention is not restricted thereto.

Wi th hydrogen under a pressure of about 200 atmospheres and at about425 C., Columbia middle-oil, which contains no useful illuminating oil,yields a product consisting of from 20 to 25 per cent of benzine -and offrom 70 to.80 per cent of a crude illuminating oil. The crudeilluminating oil which is separated oii by distillation is thenseparated by means of liquid sulphur dioxide into about 60 per' cent ofa pure illuminating oil having excellent illuminating properties andfrom 20 to 25 per cent of a product poor in hydro n, and which consistsmainly of aromatic hy rocarbons, which latter product dissolves in thesulphur dioxide. The latter product is again added to the initialmaterial (Columbia middle oil) after evaporation of the sulphur dioxideand the two together are then subjected to destructive hydrogenation.The benzines thus obtained are much better as regards theiranti-knocking properties than the benzines obtained fromlthe' initialmaterial without the said addition. The tendency of the fuel to knock isthus reduced almost by 50 per cent. Example Z A middle oil obtained bythe, destructive hydrogenation of brown coal in the presence of acatalyst comprising molybdic acid and zincoxide is subjected to afurther destructive hydrogenation at a temperature of about 450 C. andunder a pressure of about 200 'atmospheres in the presence o f acatalyst comprising a mixture of the oxldes of mo-;` lybdenum, chromiumand manganese, a mixture of oil and benzine being thus obtained, which`after separating olf the fractions of low boiling point by distillation,is separated into two portions, one of which is richer and one of whichis poorer in hydrogen, by treatment with liquidk sulphur dioxide. Theformer portion may be employed as an 1lluininating oil having the samepropertles as,

that obtained according to Exam le 1 or as the illuminating portionsobtain from natural mineral oils. The latter portion consisting ofconstituents poorer in hydrogen is conli verted by a.further-destructive hydrogenation into a gasoline which when employedas a fuel in internal combustion engines shows no tendency to knock..

" Example 3 Y A toppedfCrane Upton crude oil is subjected to destructivehydrogenation in the liquid hase under a pressure of 'about 200 atmoseresand at a temperature of about with the employmentof a colloidalcatalyst comp the oxides of' molybdenum and zinc. yields 20 to 25 vpercent of benzene ondistillation and 35 to ,40 per cent of a middleoil,rthe remainder consisting of a lubricating oil fraction.Themiddlefoil, which has the specific gravity 0.832. is split upinto twoportions by treatment with a mixture of methanol and 'cyclohexane emploed -in the proportion 4 to 1. A'portion ric er in hdrogen is thusobtained having the s i c gravity 0.820, which may, for examp e, be

employed .as anl illuminating oil and-'further 'a "portion poorer inhydr n which has the specific vity 0.910 a .which on being subjec to afurther destructive hydrogenation yields a gasoline which when employedas a fuel in internal combustion engines Ais proof against l Example 4 Amiddle oil having the specific gravity 0.838 at a temperature of 15 C.which has cent of methanol yields an oil having the* specificgravity0.831 andan oil rer. in hydrogen having the specilic'gravity0,929. The oils thus obtained are worked up andernployed in the samemanner as the products obtained according to Example2.

What we claim is 1. A process for the roduction of valuable liquid fuelsfrom iquidhydrocarbon products containing hydrocarbons of difereut,degrees of saturation with hydrogen, and which contain middle oil andconstituents of a higher order than middle oil, which comprisesseparating the constituents of the nature of middle oil from the initialhydrocarbon product, separa said constituents of the nature ofmiddle'oil into two rt-ions, one

of which is richer and one of which is poorer in hydrogen, b A treatmentlwith solvents in which the solu ility of the-said portions considerablydierent, and subjectingk the portion poor in hydrogen to a destructivehydrogenation under a pressure of atleast 50 e product thus obtained Yatmospheres, thereby producing a nonknock.

` ing motor fuel. Y

2. A rocess for the production of valuable uid els from a middle oilobtained by destructive hydro tion of hydrocarbon products and whicconsists of hydrocarbons of diiferent degrees -of saturation withhydrogen, which comprises separating said middle oil into two portions,one of which is rer and one of which richer in hy (tigen, by treatmentwith liquid sulphur dioxi e and subjecting the portion poor in hydrogento a further destructive hydrogenation under a pressure of atleast 50 atmoslfilllielres, thereby producing a non-knocke mg. A rocess for theroduction of valuable liquid prises separating said middle oils into twofractions, one of which is richer and `one poorer in hydrogen, bytreatment with a solvent in which the solubility of the said portions isconsiderably diiferent, a'nd subjecting the rtion poor in hydrogen todestructive hy rogenation under a pressure of at least 50 atmos herestoproduce a non-knocking motor fuel 7 4. A rocess for the roduction ofvaluble liquid els vfrom` mi dle oils which comprises separating saidmiddle oils into two portions, one o poorer in hydrogen, by treatmentwith solvents in which the solubility of the said portions isconsiderably dierent and ,subjecting the portion poorer in hydrogentogether with other carbonaceous substances to destructive hydrogenationunder a pressure of at least 50 atmospheres to produce a non-knockingmotor fuel.

5. A. rocess for the roduction of valuable liquid uels from mi dle oilswhich comels from mi dle oils which comwhichA is richer and one Y prisesseparating said middle oils into two l portions, one of which isriclierand one poorer in hydrogen, by treatment with liquid sulphur dioxide andsub'ecting the c ion` poorer in h drogen to esctructive ydrogenation uner a pressure of at least 50 atifnospheres to produce a non-knocking'motor ucl.

6.'A process for the production of'valuable liquid fuels from middleoils which comprises separating said middle Aoils into A two portions,one of which is richer and one poorer in hydrogen, by treatment with' amixture of methanol and cyclohexane, and subjecting the sortion poorerinv hydrogen to destructivehy rogenation under a pressure of at least 50atmospheres to produce a nonknockine motor fuel. Y

7. A process for the production of valuable Y liquid fuels from middleoils which comprises separating said middle oils into two portions, oneof which is richer and one poorer in hydrogen, by treatment with amixture of ammonia and methanol, and subjecting the portion poorer inhydrogen destructive hydrogenation under a Aof at least 50- atmospheresto produce a non-knocking motor fuel.

5 In testimony whereof we have hereunto set our hands.

` MATHIAS PIER.

EUGEN vANTI-IES. AUGUST EISENHUT.

